Alkylphenol free-liquid polymeric phosphite polymer stabilizers

ABSTRACT

An alkylphenol-free liquid polymeric phosphite is described of general Structure IV illustrated below 
                         
wherein each R 1 , R 2 , R 3  and R 4  can be the same or different and independently selected from the group consisting of C 1-20  alkyl, C 3-22  alkenyl, C 6-40  cycloalkyl, C 7-40  cycloalkylene, C 1-20  methoxy alkyl glycol ethers, C 1-20  alkyl glycol ethers, and or Y—OH; Y is selected from the group consisting of C 2-40  alkylene, C 2-40  alkyl lactone, —R 7 —N(R 8 )—R 9 —, wherein R 7 , R 8  and R 9  are independently selected from the group previously defined for R 1 , R 2 , R 3  and R 4 , now further including H; m is an integral value ranging from 2 to 100 inclusive; and x is an integral value ranging from 1 to 1,000. The alkylphenol-free liquid polymeric phosphite is useful in reducing phosphite migration within polymers.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to and incorporates by reference,pending U.S. Patent Application Ser. No. 61/306,014 filed on 19 Feb.2010.

TECHNICAL FIELD

The invention described herein pertains generally to an improved polymercomposition which contains at least one liquid polymeric phosphiteadditive which is selected from the group of all alkyl polymericphosphites as antioxidant additives and a method for the preparationthereof.

BACKGROUND OF THE INVENTION

At least one purpose associated with the addition of a stabilizer to apolymeric resin is to prevent deterioration of the polymers derived fromthe resin during processing at high temperatures and also to permit themanufacture of products with increased intrinsic quality attributable atleast in part to increased resistance to thermal and light degradationduring their intended use.

Many organic phosphites have been used as stabilizers, and most arebased on alkylphenols. Among them are the commercially significantphosphites, tris(nonylphenyl)phosphite (TNPP) andtris(2,4-di-t-butylphenyl)phosphite. Historically, TNPP has been theprimary low cost liquid phosphite stabilizer used in the plastic andrubber industry. Recently, however, plastic and rubber manufactures havebeen reluctant to use TNPP in their formulation due to concerns that oneof the degradation product of TNPP (nonylphenol) may be xenoestrogen.

U.S. Pat. No. 6,541,549 B2 and U.S. Pat. No. 7,199,170 B2 disclosephosphite compounds having a general Structure I as non-xenoestrogenicstabilizers for polymers, although they are still based on analkylphenol.

U.S. Pat. No. 7,186,853 B2 discloses phosphites comprising substitutedor unsubstituted tricyclodecylmethyl groups. The phosphites disclosedalso comprise certain alcohols which can be aliphatic, arylalkyl andalkylaryl.

U.S. Pat. No. 7,468,410 B2 and WO 07 009,916 disclosetris-(mono-alkyl)phenyl phosphites or a mixture of the general StructureII where each R is the same or different alkyl group having 1 to 8carbon atoms. Again this is a low molecular weight monophosphite stillbased on an alkylphenol.

The problem with the mono phosphites or lower molecular weightphosphites described in the mentioned patents are that, the phosphitesare still based on an alkylphenol of some type and lower molecularweight phosphites can be extracted easily from the polymer. Alkylphenolsare of concern as potential skin irritants or having xenoestrogenicactivity. Being easily extracted from a polymer means the phosphite orits degradation products can easily migrate into foods that come intocontact with polymer that maybe stabilized with the lower molecularweight or mono phosphites.

WO 08 028,858 discloses liquid polymeric phosphites of the generalstructure III wherein L is a linkage between the repeated unit n,comprising C₁-C₂₄ alkylene, C₂-C₂₄ alkenylene, and oxygen, sulfur orsubstituted nitrogen (N—R) interrupted C₂-C₂₄ alkenylene. The integer mis 0 and 1.

A disadvantage of the polymeric phosphites of this disclosure is thatall the polymeric phosphites are based on an alkylphenol of some type.It is preferable to have a polymeric phosphite that does not contain analkylphenol.

SUMMARY OF THE INVENTION

The present invention is directed to novel liquid polymeric phosphitesof the general Structure IV as stabilizers for polymers duringprocessing.

wherein

-   -   each R¹, R², R³ and R⁴ can be the same or different and        independently selected from the group consisting of C₁₋₂₀ alkyl,        C₃₋₂₂ alkenyl, C₆₋₄₀ cycloalkyl, C₇₋₄₀ cycloalkylene, C₁₋₂₀        methoxy alkyl glycol ethers, C₁₋₂₀ alkyl glycol ethers, and or        Y—OH (serving as an end capping moiety)    -   Y is selected from the group consisting of C₂₋₄₀ alkylene, C₂₋₄₀        alkyl lactone, (e.g., ethylene, propylene, caprylactone),        —R⁷—N(R⁸)—R⁹— (e.g., C₂₋₄₀ alkyl diamines and C₂₋₄₀ alkyl        triamines),        -   wherein R⁷, R⁸ and R⁹ are independently selected from the            group previously defined for R¹, R², R³ and R⁴, now further            including H;    -   m is an integral value ranging from 2 to 100 inclusive; and    -   x is an integral value ranging from 1 to 1,000.

Depending on reaction conditions and components, it is also possible tosynthesize Structure V, and be within the scope of this invention:

wherein

-   -   each R¹, R², R³ and R⁴ are as defined previously;    -   Y is as defined previously; and    -   m is as defined previously.

The novel, polymeric phosphites of the general Structures IV or V aresuitable for stabilization of organic materials against oxidative,thermal or actinic degradation.

The most preferred polymeric diphosphites or polymeric phosphites arethe ones that do not have or contain aromatic groups or alkylphenolgroups.

The advantages of the liquid high molecule weight dimeric and thepolymeric phosphites are very low volatility, no migration out of thepolymer being stabilized, very difficult to extract from the polymerbeing stabilized. These advantages can translate into no plate outduring polymer extrusion (no die lip build up) and no migration intofood from polymers that are used in food packaging. It is extremelyadvantageous to have a liquid polymeric phosphite that has excellenthydrolytic stability and one that is not based on alkylphenols.

These and other objects of this invention will be evident when viewed inlight of the drawings, detailed description and appended claims.

DETAILED DESCRIPTION OF THE INVENTION

The best mode for carrying out the invention will now be described forthe purposes of illustrating the best mode known to the applicant at thetime of the filing of this invention. The examples and figures areillustrative only and not meant to limit the invention, as measured bythe scope and spirit of the claims.

As used herein, and unless otherwise stated, the term “alkyl” meansstraight and branched chain saturated acyclic hydrocarbon monovalentgroups; said alkyl group may further optionally include one or moresuitable substituents independently selected from the group consistingof amino, halogen, hydroxy, sulfhydryl, haloalkyl, alkoxy and the like.Specific non-limiting examples of straight-chain or branched alkylgroups are C₁₋₂₀ alkyls, e.g., methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and stearylgroups. It is recognized that the alkyl may be interrupted with oxygen,sulfur or nitrogen, examples for which include: CH₃—O—CH₂CH₂—,CH₃—S—CH₂CH₂—, CH₃—N(CH₃)—CH₂CH₂—, CH₃—O—CH₂—O—CH₂CH₂—,CH₃—(O—CH₂CH₂—)₂O—CH₂CH₂—, CH₃—(O—CH₂CH₂—)₃O—CH₂CH₂— orCH₃—(O—CH₂CH₂—)₄O—CH₂CH₂—.

As used herein, and unless otherwise stated, the term “alkenyl” meansstraight and branched chain unsaturated acyclic hydrocarbon monovalentgroups; said alkenyl group may further optionally include one or moresuitable substituents independently selected from the group consistingof amino, halogen, hydroxy, sulfhydryl, haloalkyl, alkoxy and the like.Specific non-limiting examples of the straight-chain or branched alkenylgroups are those having 2 to 30 carbon atoms wherein the position of thedouble bond may vary, such as butenyl, pentenyl, hexenyl, heptenyl,octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl,tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, and octadecenylgroups. It is once again, recognized that the alkenyl may be interruptedwith oxygen, sulfur or nitrogen, examples for which include:—CH₂—O—CH₂—, —CH₂—S—CH₂—, —CH₂—N(CH₃)—CH₂—, —CH₂—O—CH₂CH₂—,—CH₂CH₂—O—CH₂CH₂—, —CH₂CH₂—O—CH₂CH₂—O—CH₂CH₂—,—CH₂CH₂—(O—CH₂CH₂—)₂O—CH₂CH₂—, —CH₂CH₂—(O—CH₂CH₂—)₃O—CH₂CH₂—,—CH₂CH₂—(O—CH₂CH₂—)₄O—CH₂CH₂—, —CH₂CH₂—S—CH₂CH₂— or—CH₂CH₂—N(CH₃)—CH₂CH₂—.

As used herein, and unless otherwise stated, the terms “cycloaliphatic”refer to a mono- or polycyclic saturated hydrocarbon monovalent grouphaving from 3 to 10 carbon atoms, or a C₇₋₁₀ polycyclic saturatedhydrocarbon monovalent group having from 7 to 10 carbon atoms. Specificnon-limiting examples of the cycloaliphatic or cyclic alkyl groups whichmay have substituents are cycloalkyl groups having 5 to 7 carbon atomssuch as cyclopentyl, cyclohexyl and cycloheptyl groups, and thealkylcycloalkyl groups having 6 to 11 carbon atoms wherein the positionof the alkyl group may vary, such as methylcyclopentyl, dimethylcyclopentyl, methylethylcyclopentyl, dim ethylcyclopentyl,methylcyclohexyl, dimethylcyclohexyl, methylethylcyclohexyl,diethylcyclohexyl, methylcycloheptyl, dimethylcycloheptyl,methylcycloheptyl, and diethylcycloheptyl groups. It is once again,recognized that the cycloaliphatic may be interrupted with oxygen,sulfur or nitrogen.

As used herein, and unless otherwise stated, the term “heterocyclic”means a mono- or polycyclic, saturated or mono-unsaturated orpoly-unsaturated monovalent hydrocarbon group having from 2 up to 15carbon atoms and including one or more heteroatoms in one or more rings,each of said rings having from 3 to 10 atoms (and optionally furtherincluding one or more heteroatoms attached to one or more carbon atomsof said ring, for instance in the form of a carbonyl or thiocarbonyl orselenocarbonyl group, and/or to one or more heteroatoms of said ring,each of said heteroatoms being independently selected from the groupconsisting of nitrogen, oxygen, sulfur, selenium and phosphorus,heterocyclic groups, including all possible isomeric forms thereof,wherein each carbon atom of said heterocyclic ring may be independentlysubstituted with a substituent selected from the group consisting ofhalogen, nitro, C₁₋₇ alkyl (such as above defined, in particularmethyl), C₃₋₇ alkenyl, trifluoromethyl, C₃₋₁₀ cycloalkyl, hydroxyl,sulfhydryl, C₁₋₇ alkoxy (such as above defined, in particular methoxy),thio C₁₋₇ alkyl, thio C₃₋₁₀ cycloalkyl, cyano, carboxylic acid oresters. depending upon the number of unsaturations in each of saidrings, heterocyclic groups may be sub-divided into heteroaromatic (or“heteroaryl”) groups and non-aromatic heterocyclic groups; when aheteroatom of the said non-aromatic heterocyclic group is nitrogen, thelatter may be substituted with a substituent selected from the groupconsisting of C₁₋₇ alkyl, C₃₋₁₀ cycloalkyl, aryl, arylalkyl andalkylaryl (each of said groups being as defined herein).

As used herein, and unless otherwise stated, the term “alkoxy” refer tosubstituents wherein an alkyl group is attached to an oxygen atomthrough a single bond.

As used herein, and unless otherwise stated, the terms “halo” or“halogen” means any atom selected from the group consisting of fluoro,chloro, bromo and iodo.

As used herein, and unless otherwise stated, the term “acyl” refers to asubstituent derived from an acid such as an organic monocarboxylic acid,a carbonic acid, a carbamic acid (resulting into a carbamoylsubstituent) or the thioacid or imidic acid (resulting into acarbamidoyl substituent) corresponding to said acids, wherein said acidscomprise an aliphatic, aromatic or heterocyclic group in the molecule. Amore specific kind of “acyl” group within the scope of the abovedefinition refers to a carbonyl (oxo) group adjacent to an alkyl, acycloalkyl, an aryl, an arylalkyl or a heterocyclic group, all of thembeing such as herein defined.

The present invention is directed to novel liquid polymeric phosphitesof the general Structure IV as stabilizers for polymers duringprocessing.

wherein

-   -   each R¹, R², R³ and R⁴ can be the same or different and        independently selected from the group consisting of C₁₋₂₀ alkyl,        C₃₋₂₂ alkenyl, C₆₋₄₀ cycloalkyl, C₇₋₄₀ cycloalkylene, C₁₋₂₀        methoxy alkyl glycol ethers, C₁₋₂₀ alkyl glycol ethers, and or        Y—OH (serving as an end capping moiety);    -   Y is selected from the group consisting of C₂₋₄₀ alkylene, C₂₋₄₀        alkyl lactone, (e.g., ethylene, propylene, caprylactone),        —R⁷—N(R⁸)—R⁹— (e.g., C₂₋₄₀ alkyl diamines and C₂₋₄₀ alkyl        triamines),        -   wherein R⁷, R⁸ and R⁹ are independently selected from the            group previously defined for R¹, R², R³ and R⁴, now further            including H;    -   m is an integral value ranging from 2 to 100 inclusive; and    -   x is an integral value ranging from 1 to 1,000.

Depending on reaction conditions and components, it is also possible tosynthesize Structure V, and be within the scope of this invention:

wherein

-   -   each R¹, R², R³ and R⁴ are as defined previously;    -   Y is as defined previously; and    -   m is as defined previously.

Synthesis of the compositions typically involve transesterification inwhich triphenyl phosphite (or any other suitable alkyl or arylphosphite) is allowed to react with an alkyl or alkenyl alcohol orpolyethylene or polypropylene glycol-ether and a diol or a polymericdiol H(OY)_(m)OH wherein Y and m are as previously defined with asuitable base catalyst at temperature between 20° C. and 250° C., andmore preferred at temperature between 50° C. and 185° C. Non-limitingexamples of mono alkyl or alkenyl alcohols include: decyl, isodecyl,lauryl, tridecyl, isotridecyl, myristyl, pentdecyl, palmyl, stearyl,isotearyl, oleic alcohol, momo hydroxyl glcolethers, etc.

Suitable base catalysts include sodium hydroxide, sodium methoxide,sodium phenolate, potassium hydroxide, and potassium carbonate. Theamount of the base catalyst used is within the range of 0.01 to 10weight percent based on the total amount of reactants charged. In apreferred embodiment, the amounts are within 0.1 to 1.0 weight percentof the reactants.

The mole ratio of alkyl alcohol or glycol-ether (containing noalkylphenols) and a polymeric diol used in forming the diphosphite ofgeneral Structures IV or V, with regard to triphenyl phosphite, is fromabout 1.9 to 2.2 moles of the phenol or alcohol or glycol-ether per moleof triphenyl phosphite and 0.3 to 0.6 mole of the diol per mole oftriphenyl phosphite. In a preferred embodiment, the mole ratio is 2.0 to1.0 of an alkyl or alkenyl alcohol or a glycol ether per mole oftriphenyl phosphite and the mole ratio of a diol to triphenyl phosphiteis 0.5 to 1.0.

The structure composition of the polymeric phosphites of the StructureIV depends on the reaction conditions, for example the temperature, thesequence how the reactants are added, alkyl or alkenyl alcohol or glycolether or a mixture or alkyl or alkenyl alcohol or glycol ether or acombination of some or all are used, the mole ratio and theconcentration of the alkyl or alkenyl alcohols or glycol ether and thepolymeric diols, and the molecular weight of the polymeric diols chosen.For example, the phosphorus content of the polymeric phosphite can beadjusted by the molecular weight of the diol and the alkyl or alkenylalcohol or glycol ether chosen. The viscosity of the polyphosphite,again, can be adjusted by the molecular weight, the length and thestructure, whether it is straight or branched, of the diol used, and aswell as the molecular weight of the phenol alkyl or alkenyl alcohol orglycol ether used.

The preferred alkyl alcohols used are C₁₂ to C₁₈. The preferred alkenylalcohols used are the C₁₆ and C₁₈. And the preferred glycol ethers usedare Carbowax 350 (monomethylether of polyethylene glycol MW 350, andtripropylene glycol monobutylether.

The polymeric diols used in the process are those which are commerciallyavailable, known as poly glycols. The preferred poly glycols arepolyethylene or polypropylene glycols, having molecular weight rangingfrom 200 to 3000, and existing as liquids at room temperature. The mostpreferred are polyethylene glycols, having molecular weight 300 to 400,and polypropylene glycols, having molecular weight of 300 to 1000.

The polymeric diphosphites of the general Structure IV and the polymericphosphites of general Structure V are suitable for stabilization oforganic materials against oxidative, thermal or actinic degradation.

The organic materials are preferably synthetic polymers. Non-limitingillustrative examples of such polymers include:

Polymers of monoolefins and diolefins for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymersof cycloolefins, for instance of cyclopentene or norbornene,polyethylene (which optionally can be crosslinked), for example highdensity polyethylene (HDPE), high density and high molecular weightpolyethylene (HDPE-HMW), high density and ultrahigh molecular weightpolyethylene (HDPE-UHMW), medium density polyethylene (MDPE), lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),(VLDPE) and (ULDPE), and blends of the polymers described above,regardless of the method of preparation.

Mixtures of the polymers above, for example, mixtures of polypropylenewith polyisobutylene, polypropylene with polyethylene (for examplePP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (forexample LDPE/HDPE).

Copolymers of monoolefins and diolefins with each other or with othervinyl monomers such as ethylene/propylene copolymers, linear low densitypolyethylene (LLDPE) and mixtures thereof with low density polyethylene(LDPE), propylene/but-1-ene copolymers, propylene/isobutylenecopolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers,ethylene/methylpentene copolymers, ethylene/heptene copolymers,ethylene/octene copolymers, ethylene/vinylcyclohexane copolymers,ethylene/cycloolefin copolymers (e.g. ethylene/norbornene like COC),ethylene/1-olefins copolymers, where the 1-olefin is generated in-situ;propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/vinylcyclohexene copolymers, ethylene/alkyl acrylatecopolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinylacetate copolymers or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedpreviously, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

Hydrocarbon resins, (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

Homopolymers and copolymers from the above and which may have anystereostructure including syndiotactic, isotactic, hemi-isotactic oratactic. Stereoblock polymers are also included.

Polystyrene and poly(p-methylstyrene) and poly(α-methylstyene).

Aromatic homopolymers and copolymers derived from vinyl aromaticmonomers including styrene, α-methylstyrene, all isomers of vinyltoluene, especially p-vinyltoluene, all isomers of ethyl styrene, propylstyrene, vinyl biphenyl, vinyl naphthalene, and vinyl anthracene, andmixtures thereof. Homopolymers and copolymers may have anystereostructure including syndiotactic, isotactic, hemi-isotactic oratactic. Stereoblock polymers are also included. Copolymers areincluded, such as vinyl aromatic monomers and comonomers selected fromethylene, propylene, dienes, nitriles, acids, maleic anhydrides,maleimides, vinyl acetate and vinyl chloride or acrylic derivatives andmixtures thereof, for example styrene/butadiene, styrene/acrylonitrile,styrene/ethylene (interpolymers), styrene/alkyl methacrylate,styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate,styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate;mixtures of high impact strength of styrene copolymers and anotherpolymer, for example a polyacrylate, a diene polymer or anethylene/propylene/diene terpolymer; and block copolymers of styrenesuch as styrene/butadiene/styrene, styrene/isoprene/styrene,styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.Hydrogenated aromatic polymers derived from hydrogenation of polymersmentioned above are included, especially includingpolycyclohexylethylene (PCHE) prepared by hydrogenating atacticpolystyrene, often referred to as polyvinylcyclohexane (PVCH). Furtherincluded are hydrogenated aromatic polymers derived from hydrogenationof polymers mentioned previously. The homopolymers and copolymers mayhave any stereostructure including syndiotactic, isotactic,hemi-isotactic or atactic. Stereoblock polymers are also included.

Graft copolymers of vinyl aromatic monomers, such as styrene orα-methylstyrene, for example styrene on polybutadiene, styrene onpolybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styreneand acrylonitrile (or methacrylonitrile) on polybutadiene; styrene,acrylonitrile and methyl methacrylate on polybutadiene; styrene andmaleic anhydride on polybutadiene; styrene, acrylonitrile and maleicanhydride or maleimide on polybutadiene; styrene and maleimide onpolybutadiene; styrene and alkyl acrylates or methacrylates onpolybutadiene; styrene and acrylonitrile on ethylene/propylene/dieneterpolymers; styrene and acrylonitrile on polyalkyl acrylates orpolyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadienecopolymers, as well as mixtures thereof with the copolymers listedabove, for example the copolymer mixtures known as ABS, MBS, ASA or AESpolymers.

Halogen-containing polymers such as polychloroprene, chlorinatedrubbers, chlorinated and brominated copolymer of isobutylene-isoprene(halobutyl rubber), chlorinated or sulfo-chlorinated polyethylene,copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogen-containing vinylcompounds, for example polyvinyl chloride, polyvinylidene chloride,polyvinyl fluoride, polyvinylidene fluoride, as well as copolymersthereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate or vinylidene chloride/vinyl acetate copolymers. such as styreneon polybutadiene, styrene and alkylacrylates or methacrylates onbutadiene, styrene and acrylonitrile on ethylene/propylene/dieneterpolymers, styrene and acrylonitrile on polyacrylates orpolymethacrylates, styrene and acrylonitrile on acrylate/butadienecopolymers, and copolymer blends known as ABS, MBS, and AES polymers.

Polymers derived from α,β-unsaturated acids and derivatives thereof suchas polyacrylates and polymethacrylates; polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.

Copolymers of the monomers mentioned in the preceding paragraph witheach other or with other unsaturated monomers, for exampleacrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylatecopolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinylhalide copolymers or acrylonitrile/alkyl methacrylate/butadieneterpolymers.

Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned above.

Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

Polyacetals such as polyoxymethylene and those polyoxymethylenes whichcontain ethylene oxide as a comonomer; polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxideswith styrene polymers or polyamides.

Polyurethanes derived from hydroxyl-terminated polyethers, polyesters orpolybutadienes on the one hand and aliphatic or aromatic polyisocyanateson the other, as well as precursors thereof.

Polyamides and copolyamides derived from diamines and dicarboxylic acidsand/or from aminocarboxylic acids or the corresponding lactams, forexample polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6,12/12, polyamide 11, polyamide 12, aromatic polyamides starting fromm-xylene diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids,polyhydantoins and polybenzimidazoles.

Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate(PAN) and polyhydroxybenzoates, as well as block copolyether estersderived from hydroxyl-terminated polyethers; and also polyestersmodified with polycarbonates or MBS.

Polycarbonates and polyester carbonates.

Polysulfones, polyether sulfones and polyether ketones.

Crosslinked polymers derived from aldehydes on the one hand and phenols,ureas and melamines on the other hand, such as phenol/formaldehyderesins, urea/formaldehyde resins and melamine/formaldehyde resins.

Drying and non-drying alkyd resins.

Unsaturated polyester resins derived from copolyesters of saturated andunsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

Crosslinkable acrylic resins derived from substituted acrylates, forexample epoxy acrylates, urethane acrylates or polyester acrylates.

Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, isocyanates, isocyanurates,polyisocyanates or epoxy resins.

Crosslinked epoxy resins derived from aliphatic, cycloaliphatic,heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidylethers of bisphenol A and bisphenol F, which are crosslinked withcustomary hardeners such as anhydrides or amines, with or withoutaccelerators.

Natural polymers such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, for example cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as rosins and their derivatives.

Blends and alloys of the aforementioned polymers (polyblends), forexample PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS,PC/ABS, PC/Polyester, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates,POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS,PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABSor PBT/PET/PC.

Naturally occurring and synthetic organic materials which are puremonomeric compounds or mixtures of such compounds, for example mineraloils, animal and vegetable fats, oil and waxes, or oils, fats and waxesbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates) and also mixtures of synthetic esters with mineral oilsin any weight ratios, typically those used as spinning compositions, aswell as aqueous emulsions of such materials.

Aqueous emulsions of natural or synthetic rubber, e.g. natural latex orlatices of carboxylated styrene/butadiene copolymers.

In general the polymeric diphosphites and the polymeric phosphites ofthis invention are added to the organic material to be stabilized inamounts from about 0.001 wt % to about 5 wt % of the weight of theorganic material to be stabilized. A more preferred range is from about0.01% to 2.0%. The most preferred range is from 0.025% to 1%.

The stabilizers of this invention may be incorporated into the organicmaterials at any convenient stage prior to manufacture of the shapedarticle using techniques known in the art.

The stabilized polymer compositions of the invention may also containfrom about 0.001% to 5%, preferably from 0.01% to 2%, and mostpreferably from 0.025% to 1% of other conventional stabilizers, anon-limiting exemplary list is provided below.

Hindered phenolic antioxidants such as 2,6-di-tert-butyl-4-methylphenol;octadecyl 3,5-di-tert-butyl-4-hydroxy-hydrocinnamate; tetrakis methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)methane; andtris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanate.

Thioesters, a non-limiting exemplary list including dilaurylthiodipropionate and distearyl thiodipropionate.

Aromatic amine stabilizers, a non-limiting exemplary list including asN,N′-diphenyl-p-phenylene-diamine.

Hindered amine light stabilizers, known as HALS, a non-limitingexemplary list including bis-(2,2,6,6-tetramethylpiperidyl)sebacate,condensation product ofN,N′-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and4,4-octylamino-2,6-dichloro-s-triazine, and the condensation product ofN,N′-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and4-N-morpholinyl-2,6-dichloro-s-triazine.

UV absorbers, a non-limiting exemplary list including2-hydroxy-4-n-octyloxybenzophenone,2(2′-hydroxy-5′-methylphenyl)-benzotriazole, and2(2′-hydroxy-5-t-octylphenyl)-benzotriazole.

Phosphites, a non-limiting exemplary list includingtris(2,4-di-tert-butylphenyl)phosphite, distearyl pentaerythritoldiphosphite, and 2,4-dicumylphenyl pentaerythritol diphosphite.

Acid neutralizers, a non-limiting exemplary list including calciumstearate, zinc stearate, calcium lactate, calcium stearyl lactate,epoxidized soybean oil, and hydrotalcite (natural and synthetic).

Other additives such as lubricants, antistatic agents, antiblockingagents, slip agents, fire retardants, nucleating agents, impactmodifiers, blowing agents, plasticizers, fillers, dyes, and pigments maybe used in an amount appropriate and in combination of the inventedpolymeric diphosphites to modify a selected property of the polymer,such as alkanolamines, a non-limiting exemplary list includingtriethanolamine and triisopropanolamine.

The novel, polymeric phosphites of the structures IV and V can be usedin particular with combination of phenolic antioxidants, lightstabilizers and/or processing stabilizers.

In addition to the liquid polymeric compounds of the formulas IV and V,the novel compositions can comprise further additives, such as forexample the following:

Antioxidants:

Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol,2-tert-butyl-4,6-di-methylphenol, 2,6-di-tert-butyl-4-ethylphenol,2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol,2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethyl-phenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example 2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol,2,4-dimethyl-6-(1′-methylheptadec-1′yl)phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.

Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctyl-thiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.

Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxy-phenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade-cyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.

Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (vitamin E).

Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)-disulfide.

Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)-phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butyl-phenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyI)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

O-, N- and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate,di-dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

Aromatic hydroxybenzyl compounds, for example1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-benzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

Triazine compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy-anilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzypisocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

Benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.

Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- orpolyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol,1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol,neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethyleneglycol, pentaerythritol, tris(hydroxyethyl)isocyanurate,N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol,trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)trimethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide.

Ascorbic acid (vitamin C).

Aminic antioxidants, for example N,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- and dialkylatedtert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylatedtert-octylphenothiazines, N-allylphenothiazine,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis(2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

UV absorbers and light stabilizers

2-(2′-Hydroxyphenyl)benzotriazoles, for example2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol];the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300; —[R—CH₂CH₂—COO—CH₂CH₂]₂—, whereR=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl,2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)phenyl]-benzotriazole;2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyI)-5′-(α,α-dimethylbenzyl)phenyl]benzotriazole.

2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxyand 2′-hydroxy-4,4′-dimethoxy derivatives.

Esters of substituted and unsubstituted benzoic acids, for example4-tert-butylphenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol,benzoyl resorcinol, 2,4-di-tert-butylphenyl,3,5-di-tert-butyl-4-hydroxybenzoate,hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate,octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate,2-methyl-4,6-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate.

Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate,isooctyl-α-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate,methyl α-cyano-β-methyl-p-methoxycinnamate, butylα-cyano-β-methyl-p-methoxycinnamate, methylα-carbomethoxy-p-methoxycinnamate and N-(β-carbomethoxyβ-cyanovinyl)-2-methylindoline.

Nickel compounds, for example nickel complexes of2,2′-thiobis[4-(1,1,3,3-tetramethyl-butyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

Stericallv hindered amines, for examplebis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethyl-piperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cycliccondensates of N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, the condensate of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensate of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine, a condensate of1,6-hexanediamine and 2,4,6-trichloro-1,3,5-triazine as well asN,N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine,N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-di-aza-4-oxo-spiro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decaneand epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,a diester of 4-methoxymethylenemalonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, areaction product of maleic acid anhydride-α-olefin copolymer with2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine.

Oxamides, for example 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide,2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

2-(2-Hydroxyphenyl)-1,3,5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl-phenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-ethylethoxy)phenyl]-4,6-diphenyl-1,3,5-triazine.

Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide,N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

Phosphites and phosphonites, for example triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites,tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,distearylpentaerythritol diphosphite,tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritoldiphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,4-di-cumylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,2,2′,2″-nitrilo-[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,r-bi[rho]henyl-2,2′-diyl)phosphite],2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite,5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.

Phosphines, for example 1,3-bis(diphenylphosphino)-2,2-dimethyl-propane.

Hydroxylamines, for example N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

Nitrones, for example N-benzyl-α-phenylnitrone, N-ethyl-α-methylnitrone,N-octyl-α-heptylnitrone, N-lauryl-α-undecylnitrone,N-tetradecyl-α-tridecylnitrone, N-hexadecyl-α-pentadecylnitrone,N-octadecyl-α-heptadecylnitrone, N-hexadecyl-α-heptadecylnitrone,N-ocatadecyl-α-pentadecylnitrone, N-heptadecyl-α-hepta-decylnitrone,N-octadecyl-α-hexadecylnitrone, nitrone derived fromN,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

Thiosynemists, for example dilauryl thiodipropionate or distearylthiodipropionate.

Peroxide scavengers, for example esters of p-thiodipropionic acid, forexample the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercapto-benzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis((3-dodecylmercapto)propionate.

Polvamide stabilizers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

Basic co-stabilizers, for example melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids, for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or zincpyrocatecholate.

Nucleating agents, for example inorganic substances, such as talcum,metal oxides, such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, preferably, alkaline earth metals; organiccompounds, such as mono- or polycarboxylic acids and the salts thereof,e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodiumsuccinate or sodium benzoate; polymeric compounds, such as ioniccopolymers (ionomers), e.g.,1,3:2,4-bis(3′,4′-dimethylbenzylidene)sorbitol,1,3:2,4-di(paramethyldibenzylidene)sorbitol, and1,3:2,4-di(benzylidene)sorbitol.

Fillers and reinforcing agents, for example calcium carbonate,silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica,barium sulfate, metal oxides and hydroxides, carbon black, graphite,wood flour and flours or fibers of other natural products, syntheticfibers.

Other additives, for example plasticizers, lubricants, emulsifiers,pigments, rheology additives, catalysts, flow-control agents, opticalbrighteners, flameproofing agents, antistatic agents blowing agents andinfrared (IR) adsorbers. Preferred IR absorbers are for examplepigments, dyes or organometallic compounds.

Benzofuranones and indolinones, such as3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butylbenzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyl-oxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)-benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one or3-(2-acetyl-5-isooctylphenyl)-5-isooctylbenzofuran-2-one.

The synthetic polymers prepared in this way can be employed in a widevariety of forms, for example as foams, films, fibers, tapes, moldingcompositions, as profiles or as binders for coating materials,especially powder coatings, adhesives, putties or especially asthick-layer polyolefin moldings which are in long-term contact withextractive media, such as, for example, pipes for liquids or gases,films, fibers, geomembranes, tapes, profiles or tanks.

In one non-limiting embodiment, the preferred thick-layer polyolefinmoldings have a layer thickness of from 1 to 50 mm, in particular from 1to 30 mm, for example from 2 to 10 mm.

The compositions according to the invention can be advantageously usedfor the preparation of various shaped articles. An exemplarynon-limiting list of end-use applications include, but are not limitedto: Floating devices, marine applications, pontoons, buoys, plasticlumber for decks, piers, boats, kayaks, oars, and beach reinforcements;Automotive applications, in particular bumpers, dashboards, battery,rear and front linings, moldings parts under the hood, hat shelf, trunklinings, interior linings, air bag covers, electronic moldings forfittings (lights), panes for dashboards, headlamp glass, instrumentpanel, exterior linings, upholstery, automotive lights, head lights,parking lights, rear lights, stop lights, interior and exterior trims;door panels; gas tank; glazing front side; rear windows; seat backing,exterior panels, wire insulation, profile extrusion for sealing,cladding, pillar covers, chassis parts, exhaust systems, fuelfilter/filler, fuel pumps, fuel tank, body side moldings, convertibletops, exterior mirrors, exterior trim, fasteners/fixings, front endmodule, glass, hinges, lock systems, luggage/roof racks, pressed/stampedparts, seals, side impact protection, sound deadener/insulator andsunroof; Road traffic devices, in particular sign postings, posts forroad marking, car accessories, warning triangles, medical cases,helmets, tires; Devices for plane, railway, motor car (car, motorbike)including furnishings; Devices for space applications, in particularrockets and satellites, e.g. reentry shields; Devices for architectureand design, mining applications, acoustic quietized systems, streetrefuges, and shelters.

The invention also has applicability in: Appliances, cases and coveringsin general and electric/electronic devices (personal computer,telephone, portable phone, printer, television-sets, audio and videodevices), flower pots, satellite TV bowl, and panel devices; Jacketingfor other materials such as steel or textiles; Devices for theelectronic industry, in particular insulation for plugs, especiallycomputer plugs, cases for electric and electronic parts, printed boards,and materials for electronic data storage such as chips, check cards orcredit cards; Electric appliances, in particular washing machines,tumblers, ovens (microwave oven), dish-washers, mixers, and irons;Covers for lights (e.g. street-lights, lamp-shades); Applications inwire and cable (semi-conductor, insulation and cable-jacketing); andfoils for condensers, refrigerators, heating devices, air conditioners,encapsulating of electronics, semi-conductors, coffee machines, andvacuum cleaners.

The invention further has applicability in: Technical articles such ascogwheel (gear), slide fittings, spacers, screws, bolts, handles, andknobs; Rotor blades, ventilators and windmill vanes, solar devices,swimming pools, swimming pool covers, pool liners, pond liners, closets,wardrobes, dividing walls, slat walls, folding walls, roofs, shutters(e.g. roller shutters), fittings, connections between pipes, sleeves,and conveyor belts; Sanitary articles, in particular shower cubicles,lavatory seats, covers, and sinks; Hygienic articles, in particulardiapers (babies, adult incontinence), feminine hygiene articles, showercurtains, brushes, mats, tubs, mobile toilets, tooth brushes, and bedpans; Pipes (crosslinked or not) for water, waste water and chemicals,pipes for wire and cable protection, pipes for gas, oil and sewage,guttering, down pipes, and drainage systems; Profiles of any geometry(window panes) and siding; Glass substitutes, in particular extruded orco-extruded plates, glazing for buildings (monolithic, twin ormultiwall), aircraft, schools, extruded sheets, window film forarchitectural glazing, train, transportation, sanitary articles, andgreenhouse; Plates (walls, cutting board), extrusion-coating(photographic paper, tetrapack and pipe coating), silos, woodsubstitute, plastic lumber, wood composites, walls, surfaces, furniture,decorative foil, floor coverings (interior and exterior applications),flooring, duck boards, and tiles; Intake and outlet manifolds; andCement-, concrete-, composite-applications and covers, siding andcladding, hand rails, banisters, kitchen work tops, roofing, roofingsheets, tiles, and tarpaulins.

Still further applications include: Plates (walls and cutting board),trays, artificial grass, astroturf, artificial covering for stadiumrings (athletics), artificial floor for stadium rings (athletics), andtapes; Woven fabrics continuous and staple, fibers (carpets/hygienicarticles/geotextiles/monofilaments; filters; wipes/curtains(shades)/medical applications), bulk fibers (applications such asgown/protection clothes), nets, ropes, cables, strings, cords, threads,safety seat-belts, clothes, underwear, gloves; boots; rubber boots,intimate apparel, garments, swimwear, sportswear, umbrellas (parasol,sunshade), parachutes, paraglides, sails, “balloon-silk”, campingarticles, tents, airbeds, sun beds, bulk bags, and bags; and Membranes,insulation, covers and seals for roofs, tunnels, dumps, ponds, dumps,walls roofing membranes, geomembranes, swimming pools, curtains(shades)/sun-shields, awnings, canopies, wallpaper, food packing andwrapping (flexible and solid), medical packaging (flexible & solid),airbags/safety belts, arm- and head rests, carpets, centre console,dashboard, cockpits, door, overhead console module, door trim,headliners, interior lighting, interior mirrors, parcel shelf, rearluggage cover, seats, steering column, steering wheel, textiles, andtrunk trim.

Additional applications include: Films (packaging, dump, laminating,agriculture and horticulture, greenhouse, mulch, tunnel, silage), balewrap, swimming pools, waste bags, wallpaper, stretch film, raffia,desalination film, batteries, and connectors; Food packing and wrapping(flexible and solid), bottles; Storage systems such as boxes (crates),luggage, chest, household boxes, pallets, shelves, tracks, screw boxes,packs, and cans; and Cartridges, syringes, medical applications,containers for any transportation, waste baskets and waste bins, wastebags, bins, dust bins, bin liners, wheely bins, container in general,tanks for water/used water/chemistry/gas/oil/gasoline/diesel; tankliners, boxes, crates, battery cases, troughs, medical devices such aspiston, ophthalmic applications, diagnostic devices, and packing forpharmaceuticals blister.

Still additional applications may encompass: Extrusion coating (photopaper, tetrapack, pipe coating), household articles of any kind (e.g.appliances, thermos bottle/clothes hanger), fastening systems such asplugs, wire and cable clamps, zippers, closures, locks, andsnap-closures; Support devices, articles for the leisure time such assports and fitness devices, gymnastics mats, ski-boots, inline-skates,skis, big foot, athletic surfaces (e.g. tennis grounds); screw tops,tops and stoppers for bottles, and cans; Furniture in general, foamedarticles (cushions, impact absorbers), foams, sponges, dish clothes,mats, garden chairs, stadium seats, tables, couches, toys, building kits(boards/figures/balls), playhouses, slides, and play vehicles; Materialsfor optical and magnetic data storage; Kitchen ware (eating, drinking,cooking, storing); Boxes for CD's, cassettes and video tapes; DVDelectronic articles, office supplies of any kind (ball-point pens,stamps and ink-pads, mouse, shelves, tracks), bottles of any volume andcontent (drinks, detergents, cosmetics including perfumes), and adhesivetapes; Footwear (shoes/shoe-soles), insoles, spats, adhesives,structural adhesives, food boxes (fruit, vegetables, meat, fish),synthetic paper, labels for bottles, couches, artificial joints (human),printing plates (flexographic), printed circuit boards, and displaytechnologies; and devices of filled polymers (talc, chalk, china clay(kaolin), wollastonite, pigments, carbon black, TiO2, mica,nanocomposites, dolomite, silicates, glass, asbestos).

Still further applications may encompass are: compositions comprising ascomponent (a) fibers and fabrics used in nonwoven medical fabric andrelated apparel (surgical gowns, drapes, bandages), construction fabrics(house wrapping, roofing, swimming-pool wrapping) and home furnishing(carpets, table linens, shower curtains).

Thus, a further embodiment of the present invention relates to a shapedarticle, in particular a film, pipe, profile, bottle, tank or container,fiber containing a composition as described above.

As evident from the above, the organic materials to be protected arepreferably organic polymers, particularly synthetic polymers.Thermoplastic materials, in particular polyolefins, are particularlyadvantageously protected. In particular, the excellent effectiveness ofthe polymeric compounds of the formula IV as processing stabilizers(heat stabilizers) should be emphasized. For this purpose, they areadvantageously added to the polymer before or during processing thereof.However, other polymers (for example elastomers) or lubricants orhydraulic fluids can also be stabilized against degradation, for examplelight-induced or thermo-oxidative degradation. Elastomers are given inthe above list of possible organic materials.

At least one aspect of the present invention is therefore the use of aliquid polymeric compound of the Formula IV or Formula V or a mixture ofcompositions resulting from the synthesis of compositions covered byFormulas IV and/or V for protecting organic materials against oxidative,thermal or light-induced degradation. The novel liquid polymericcompounds are at least partially distinguished by pronounced hydrolysisstability and advantageous coloring behaviour, i.e. low discoloration ofthe organic materials during processing.

The invention will now be described by a series of examples.

EXAMPLES Example #1

The apparatus in Example #1 was used. PPG 425 (55 g, 0.129 mol),triphenyl phosphite (45 g, 0.145 mol), Carbowax 350 (a mono-methyletherpolyethylene glycol with an average MW of 350), (63 g, 0.189 mol), and0.8 grams of potassium hydroxide were added. The mixture was mixed welland heated to 160-162° C. under nitrogen and held at the temperature for1 hour. The pressure was then gradually reduced to 0.3 mmHg and thetemperature was increased to 170-172° C. over a course of 1 hour. Thereaction contents were held at 170-172° C. under the vacuum for 2 hoursat which point no more phenol was distilling out. The vacuum was thenbroken by nitrogen and the crude product was cooled to 50° C. Theproduct was a clear, colorless liquid.

Example #2

The apparatus in Example #1 was used. PPG 400 (95 g, 0.237 mol),triphenyl phosphite (73 g, 0.235 mol), a mixture of lauryl and myristylalcohol with a hydroxyl number of about 280, (47 g, 0.235 mol), and 0.8grams of potassium hydroxide were added. The mixture was mixed well andheated to 160-162° C. under nitrogen and held at the temperature for 1hour. The pressure was then gradually reduced to 0.3 mmHg and thetemperature was increased to 170-172° C. over a course of 1 hour. Thereaction contents were held at 170-172° C. under the vacuum for 2 hoursat which point no more phenol was distilling out. The vacuum was thenbroken by nitrogen and the crude product was cooled to 50° C. Theproduct was a clear, colorless liquid.

Example #3

The apparatus in Example #1 was used. PPG 400 (48 g, 0.12 mol),triphenyl phosphite (73 g, 0.235 mol), lauryl alcohol, (47 g, 0.235mol), dipropylene glycol (16 g 0.12 mol) and 0.8 grams of potassiumhydroxide were added. The mixture was mixed well and heated to 160-162°C. under nitrogen and held at the temperature for 1 hour. The pressurewas then gradually reduced to 0.3 mmHg and the temperature was increasedto 170-172° C. over a course of 1 hour. The reaction contents were heldat 170-172° C. under the vacuum for 2 hours at which point no morephenol was distilling out. The vacuum was then broken by nitrogen andthe crude product was cooled to 50° C. The product was a clear,colorless liquid.

Example #4

The apparatus in Example #1 was used. PPG 400 (50.22 g, 0.1256 mol),triphenyl phosphite (40 g, 0.129 mol), Carbowax 350 (a mono-methyletherpolyethylene glycol with an average MW of 350), (26 g, 0.074 mol),tri-isopropanol amine (4.5 g 0.023 mol), and 0.8 grams of potassiumhydroxide were added. The mixture was mixed well and heated to 160-162°C. under nitrogen and held at the temperature for 1 hour. The pressurewas then gradually reduced to 0.3 mmHg and the temperature was increasedto 170-172° C. over a course of 1 hour. The reaction contents were heldat 170-172° C. under the vacuum for 2 hours at which point no morephenol was distilling out. The vacuum was then broken by nitrogen andthe crude product was cooled to 50° C. The product was a clear,colorless liquid.

Example #5

The apparatus in Example #1 was used. PPG 400 (100 g, 0.25 mol),triphenyl phosphite (78 g, 0.2516 mol), a mixture of cetyl and stearylalcohol with a hydroxyl number of about 211, (34 g, 0.1285 mol),tripropylene glycol butylether (32 g, 0.129 mol) and 0.8 grams ofpotassium carbonate were added. The mixture was mixed well and heated to160-162° C. under nitrogen and held at the temperature for 1 hour. Thepressure was then gradually reduced to 0.3 mmHg and the temperature wasincreased to 170-172° C. over a course of 1 hour. The reaction contentswere held at 170-172° C. under the vacuum for 2 hours at which point nomore phenol was distilling out. The vacuum was then broken by nitrogenand the crude product was cooled to 50° C. The product was a clear,colorless liquid.

Example #6

The apparatus in Example #1 was used. PPG 400 (100 g, 0.25 mol),triphenyl phosphite (78 g, 0.2516 mol), a mixture of cetyl and stearylalcohol with a hydroxyl number of about 211, (34 g, 0.1285 mol), oleylalcohol (34 g, 0.126 mol) and 0.8 grams of potassium carbonate wereadded. The mixture was mixed well and heated to 160-162° C. undernitrogen and held at the temperature for 1 hour. The pressure was thengradually reduced to 0.3 mmHg and the temperature was increased to170-172° C. over a course of 1 hour. The reaction contents were held at170-172° C. under the vacuum for 2 hours at which point no more phenolwas distilling out. The vacuum was then broken by nitrogen and the crudeproduct was cooled to 50° C. The product was a clear, colorless liquid.

Example #7

The apparatus in Example #1 was used. PPG 400 (95 g, 0.237 mol),triphenyl phosphite (73 g, 0.235 mol), Neodol 23 (a blend of C₁₂ and C₁₃alcohols) (57 g, 0.266 mol) and 0.8 grams of potassium hydroxide wereadded. The mixture was mixed well and heated to 160-162° C. undernitrogen and held at the temperature for 1 hour. The pressure was thengradually reduced to 0.3 mmHg and the temperature was increased to170-172° C. over a course of 1 hour. The reaction contents were held at170-172° C. under the vacuum for 2 hours at which point no more phenolwas distilling out. The vacuum was then broken by nitrogen and the crudeproduct was cooled to 50° C. The product was a hazy, colorless liquid.

Example #8

The apparatus in Example #1 was used. PPG 400 (100 g, 0.25 mol),triphenyl phosphite (155 g, 0.5 mol), a mixture of lauryl and myristylalcohol with a hydroxyl number of about 280, (200 g, 1.0 mol), and 0.8grams of potassium hydroxide were added. The mixture was mixed well andheated to 160-162° C. under nitrogen and held at the temperature for 1hour. The pressure was then gradually reduced to 0.3 mmHg and thetemperature was increased to 170-172° C. over a course of 1 hour. Thereaction contents were held at 170-172° C. under the vacuum for 2 hoursat which point no more phenol was distilling out. The vacuum was thenbroken by nitrogen and the crude product was cooled to 50° C. Theproduct was a clear, colorless liquid.

Example #9

The apparatus in Example #1 was used. 1,6 hexane diol (57 g, 0.48 mol),triphenyl phosphite (150 g, 0.48 mol), a mixture of lauryl and myristylalcohol with a hydroxyl number of about 280, (97 g, 0.48 mol), and 0.8grams of potassium hydroxide were added. The mixture was mixed well andheated to 160-162° C. under nitrogen and held at the temperature for 1hour. The pressure was then gradually reduced to 0.3 mmHg and thetemperature was increased to 170-172° C. over a course of 1 hour. Thereaction contents were held at 170-172° C. under the vacuum for 2 hoursat which point no more phenol was distilling out. The vacuum was thenbroken by nitrogen and the crude product was cooled to 50° C. Theproduct was a hazy, colorless liquid.

Example #10

The apparatus in Example #1 was used. Poly THF 250MW (121 g, 0.48 mol),triphenyl phosphite (150 g, 0.48 mol), a mixture of lauryl and myristylalcohol with a hydroxyl number of about 280, (97 g, 0.48 mol), and 0.8grams of potassium hydroxide were added. The mixture was mixed well andheated to 160-162° C. under nitrogen and held at the temperature for 1hour. The pressure was then gradually reduced to 0.3 mmHg and thetemperature was increased to 170-172° C. over a course of 1 hour. Thereaction contents were held at 170-172° C. under the vacuum for 2 hoursat which point no more phenol was distilling out. The vacuum was thenbroken by nitrogen and the crude product was cooled to 50° C. Theproduct was a hazy, colorless liquid.

Example #11

The apparatus in Example #1 was used. Methyldiethanolamine (58 g, 0.48mol), triphenyl phosphite (150 g, 0.48 mol), a mixture of lauryl andmyristyl alcohol with a hydroxyl number of about 280, (97 g, 0.48 mol),and 0.8 grams of potassium hydroxide were added. The mixture was mixedwell and heated to 160-162° C. under nitrogen and held at thetemperature for 1 hour. The pressure was then gradually reduced to 0.3mmHg and the temperature was increased to 170-172° C. over a course of 1hour. The reaction contents were held at 170-172° C. under the vacuumfor 2 hours at which point no more phenol was distilling out. The vacuumwas then broken by nitrogen and the crude product was cooled to 50° C.The product was a hazy, colorless liquid.

Characteristics of the various synthesized additives may becharacterized at least in part by the following tables.

TABLE 1 Parameter Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9Ex. 10 Ex. 11 % P 3.7 4.9 5.9 4.7 4.5 4.4 4.8 4.9 8.9 6.4 6.4 CPS/25° C.960 3212 973 2156 3144 3894 642 215 6528 659 37282 AV 0.01 0.01 0.050.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01

TABLE 2 MW data Parameter Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 MW range1000-16,500 700-55,000 350-50,000 600-16,500 1000-55,000 800-55,000Average MW 6,125 9,111 7,250 6,155 21,243 10,666 Parameter Ex. 7 Ex. 8Ex. 9 Ex. 10 Ex. 11 MW range 1200-55,000 630-6,500 800-320,000630-16,500 850-8,000 Average MW 12,024 2,550 31,515 8,157 1,530

Polymeric phosphites of examples 1-11 are of great interest because theyare not based on alkylphenols.

The following tables detail the performance of some of the polymericphosphite stabilizers 1-18 in polyolefin's, (linear low densitypolyethylene, either Exxon or Nova LLDPE was used). These compounds showperformance as plastic stabilizers that are comparable to or better thanthat of TNPP. With regard to Melt Flow Rate (MFR), a good plasticstabilizer will contribute to a low initial MFR and then maintain thelow MFR. For Hunter b Color performance, a good plastic stabilizer willyield low initial color and then maintain that low color.

Sample Preparation

The polyolefin powders (polyethylene, LLDPE); (high density polyethyleHDPE) and (polypropylene, PP) are dry blended with the stabilizerformulation using a Warring blender. The mixer is run at approximately60 rpm or a speed which does not cause the material to splash out of thebowl for 30 seconds with shaking of blender every 5 seconds. The masterbatch is then added to a preheated co-rotating twin screw extruder wherethe plastic is homogeneously mixed. Extrusion is typically performed at260° C. The extruded plastic is cooled into a cold water bath,completely dried, and pelletized. The collected polymer pellets are theresult of the first pass extrusion and are the starting material for allsubsequent test protocols. The isolated pellets are added to theextruder repeatedly to generate the third and fifth pass material.

Melt Flow Rate Analysis

The melt flow rate was performed using the ASTM 1238-90b test methodmeasured at 21.6 Kg/190° C. The melt flow rate was complete on a TiniusOlsen extrusion plastometer.

Color Analysis

Color analysis was performed on compression molded films or plaques witha Hunter Lab Ulstrascan XE machine. Observations were made with a D65illuminant and 10° observer. Yellowness Index measurements were made inaccord with ASTM D1925-70. The lower the YI (yellowness index) thebetter the color.

Gas Fade Aging

Gas fade aging was performed based on methods in ASTM 1925 using a NOxgas oven. Analysis was performed on compression molded plaques placedinto a 60° C. nitrogen oven. Observations were made by measuringyellowness index for color development during exposure to oxides ofnitrogen.

The LLPE formulations were tested using 900 PPM of the phosphite and 500PPM of the primary antioxidant Dovernox 76 or at 1800 ppm phosphite, 300ppm Dovernox 76, zinc stearate 200 ppm and 100 ppm DHT4A were used asneutralizers.

The HDPR formulations were tested using 900 ppm phosphite, 500 ppmDovernox 76 and 500 pp calcium stearate.

The PP formulations were tested using 500 ppm phosphite, 500 ppmDovernox 10 and 500 ppm calcium stearate.

TABLE 3 LLDPE, MFI High Load Melt Flow: 190° C./21.6 Kgs (LLDPE,Phosphite at 900 ppm and 500 ppm Dovernox 76, extrusion temperature 260°C.) Polymeric Phosphite 1^(st) pass 3^(rd) pass 5^(th) pass None 15.313.6 12.8 TNPP 18.1 16.4 14.4 Ex 1 18.3 14.9 13.3 Ex. 2 18.7 17.2 15.5Ex. 4 17.1 14.4 12.9 Ex. 5 18.5 17.5 15.4 Ex. 7 18.0 16.5 14.4

The data shows that TNPP gives good MFI stability and so do thepolymeric phosphites. The polymeric phosphites either match or in somecases exceed the performance of the TNPP

TABLE 4 LLDPE YI Color Data Polymeric Phosphite 1^(st) pass 3^(rd) pass5^(th) pass none −3.7 −1.7 0.4 TNPP −4.7 −2.9 −0.1 Ex. 1 −6.2 −3.3 −1.1Ex. 2 −5.4 −2.9 0.0 Ex. 4 −4.6 −2.3 1.4 Ex. 5 −4.4 −2.6 0.6 Ex. 7 −5.3−3.9 −2.2

The polymeric phosphites closely match or exceed the performance of theTNPP in color stability (the lower the YI the better the color.

TABLE 5 Gas Fade 60° C. Using 1^(st) Pass, LLDPE, Days Phosphite 0 days6 days 12 days 19 days 22 days 29 days TNPP −1.2 7.0 26.5 34.5 362 39.6Ex. 2 −5.4 3.8 16.8 25.1 27.4 31.8 Ex. 7 −6.0 0.7 14.0 23.6 26.7 33.1

The gas fade results are better for the polymeric phosphites.

TABLE 6 High Load Melt Flow: 190° C./21.6 Kgs (HDPE: 900 ppm Phosphite,500 ppm Dovernox 76, and 500 ppm calcium stearate) Extrusion temperature260° C. Phosphite 1^(st) pass 3^(rd) pass 5^(th) pass none 25.1 22.420.8 TNPP 26.6 25.3 25.1 Ex. 2 26.1 25.8 22.9 Ex. 5 25.6 24.0 22.3

TABLE 7 Color, YI for HDPE Extrusion @ 260 C. Phosphite 1^(st) pass3^(rd) pass 5 pass none 5 9.6 12.6 TNPP 7.4 8.1 11.7 Ex. 2 −2.4 1.2 4.0Ex. 5 −1.0 1.7 4.1

The polymeric phosphites show good performance as stabilizer fo HDPEespecially for color.

TABLE 8 Melt Flow: 190° C./21.6 Kgs (Polypropylene: 500 ppm Phosphite,500 ppm Dovernox 10, and 500 ppm calcium stearate) Extrusion temperature260° C. Phosphite 1^(st) pass 2^(nd) pass 3^(rd) pass none 30.9 50.1 Toohigh TNPP 18.0 25.2 36.2 Ex. 2 20.7 26.8 39.0 Ex. 5 18.9 28.2 46.9 Ex. 2using Vitamin E in 18.25 20.9 23.2 place of Dovernox 10

TABLE 9 Color, YI (Polypropylene: 500 ppm Phosphite, 500 ppm Dovernox10, and 500 ppm calcium stearate) Extrusion temperature 260° C.Phosphite 1^(st) pass 2^(nd) pass 3^(rd) pass none 9.8 12.9 17.6 TNPP 913.4 16.6 Ex. 2 11.6 12.3 13.5 Ex. 5 5.6 9.9 13.2 Ex. 2 using Vitamin Ein 10.4 14.5 18.9 place of Dovernox 10

The polymeric phosphites show good performance as a stabilizer in PP.The use of Vitamin E as the primary anti-oxidant in place of theDovernox 10 greatly improves the MFI.

The data shows that some of the polymeric phosphites perform equal tooor better than the TNPP. Besides giving good melt flow stability andcolor stability during processing and in gas fade testing, the polymericdiphosphite and the polymeric poly-phosphites have excellentcompatibility with LLDPE and they do not migrate. Non migration isespecial important for additives that are used in polymer film orplastics that are used for food contact. Non migration also reduces ofeliminates and plate out on cooling rolls or die build up due tovolatile additives. The polymeric poly-phosphites illustrated inExamples 1, 2, 3, 4, 6, 7, and 8 are especially good polymer stabilizersfor food contact plastic since they do not contain any alkylphenols andbasically are made from raw materials that are all biodegradable.

What has been illustrated is the ability to synthesize a liquidpolymeric phosphite in which the substituent groups are essentially allaliphatic. The liquid phosphite is preferably a polyphosphite, in whichthe segments between the phosphite moieties are preferably apolyalkylene glycol, more preferably a polyethylene or a polypropyleneglycol.

The invention has been described with reference to preferred andalternate embodiments. Obviously, modifications and alterations willoccur to others upon the reading and understanding of the specification.It is intended to include all such modifications and alterations insofaras they come within the scope of the appended claims or the equivalentsthereof.

What is claimed is:
 1. An alkylphenol-free liquid polymericpolyphosphite which comprises:

wherein each R¹, R², R³ and R⁴ can be the same or different andindependently selected from the group consisting of C₁₂₋₂₀ alkyl, C₁₂₋₂₂alkenyl, C₁₂₋₄₀ cycloalkyl, C₁₂₋₄₀ cycloalkylene, C₁₂₋₂₀ methoxy alkylglycol ethers, and Y—OH as an end-capping group; each Y is independentlyselected from the group consisting of C₁₋₂₀ alkyl, C₆₋₄₀ cycloalkyl,C₇₋₄₀ cycloalkylene, C₃₋₂₀ alkyl glycol ethers, C₂₋₄₀ alkylene, C₃₋₄₀alkyl lactone, and —R⁷—N(R⁸)—R⁹—; R⁷, R⁸ and R⁹ are independentlyselected from the group consisting of C₁₋₂₀ alkyl, C₂₋₂₂ alkenyl, C₆₋₄₀cycloalkyl, C₇₋₄₀ cycloalkylene and H; m is an integral value rangingfrom 2 to 100 inclusive; and x is an integral value ranging from 1 to1,000, and further wherein said polymeric polyphosphite is a reactionproduct of: at least one monohydroxy-terminated reactant selected fromthe group consisting of R¹—OH, R²—OH, R³—OH and R⁴—OH; and at least onedihydroxy-terminated reactant selected from the group HO—Y—OH, and atrifunctional reactant comprising at least one phosphorus moiety, saidpolymeric polyphosphite having less terminal hydroxy groups than saidreaction product formed using dihydroxy-terminated reactants.
 2. Thepolymeric polyphosphite of claim 1 wherein said polymeric polyphosphiteis not based on either an aromatic phenol or an alkylphenol.
 3. Thepolymeric polyphosphite of claim 1 wherein said polymeric polyphosphiteis comprised of a polyalkylene glycol.
 4. The polymeric polyphosphite ofclaim 3 wherein said polyalkylene glycol is selected from the groupconsisting of polyethylene glycol and polypropylene glycol.
 5. Thepolymeric polyphosphite of claim 1 wherein each R¹, R², R³ and R⁴ arealiphatic, and wherein said polymeric polyphosphite further comprises analkanolamine.
 6. A process for stabilizing a polymer, as indicated byessentially matching or lowering the Yellowness Index of a polymer whencompared to a polymeric composition which does not include the additionof a tris(nonylphenyl) phosphite or the liquid polymeric polyphosphiteof formula (IV), comprising the step of adding an alkylphenol-freeliquid polymeric polyphosphite which comprises:

wherein each R¹, R², R³ and R⁴ can be the same or different andindependently selected from the group consisting of C₁₂₋₂₀ alkyl, C₁₂₋₂₂alkenyl, C₁₂₋₄₀ cycloalkyl, C₁₂₋₄₀ cycloalkylene, C₁₂₋₂₀ methoxy alkylglycol ethers, and Y—OH as an end-capping group; each Y is independentlyselected from the group consisting of C₁₋₂₀ alkyl, C₆₋₄₀ cycloalkyl,C₇₋₄₀ cycloalkylene, C₃₋₂₀ alkyl glycol ethers, C₂₋₄₀ alkylene, C₃₋₄₀alkyl lactone, and —R⁷—N(R⁸)—R⁹—; R⁷, R⁸ and R⁹ are independentlyselected from the group consisting of C₁₋₂₀ alkyl, C₂₋₂₂ alkenyl, C₆₋₄₀cycloalkyl, C₇₋₄₀ cycloalkenyl and H; m is an integral value rangingfrom 2 to 100 inclusive; and x is an integral value ranging from 1 to1,000, and further wherein said polymeric polyphosphite is a reactionproduct of: at least one monohydroxy-terminated reactantselected fromthe group consisting of R¹—OH, R²—OH, R³—OH and R⁴—OH; and at least onedihydroxy-terminated reactantselected from the group HO—Y—OH, and atrifunctional reactant comprising at least one phosphorus moiety, saidpolymeric polyphosphite having less terminal hydroxy groups than saidreaction product formed using dihydroxy-terminated reactants.
 7. Theprocess of claim 6 wherein said polymeric polyphosphite is not based oneither an aromatic phenol or an alkylphenol.
 8. The process of claim 6wherein said polymeric polyphosphite is comprised of a polyalkyleneglycol.
 9. The process of claim 8 wherein said polyalkylene glycol isselected from the group consisting of polyethylene glycol andpolypropylene glycol.
 10. The process of claim 6 wherein each R¹, R², R³and R⁴ are aliphatic; and wherein said polymeric polyphosphite furthercomprises an alkanolamine.
 11. The process of claim 6 which comprises:adding between 0.01-2 weight percent of said polymeric polyphosphite toat least one polymer.
 12. The process of claim 11 wherein said polymeris a carbon-based polymer.
 13. The process of claim 11 which furthercomprises the step of adding at least one other additive selected fromthe group consisting of a hindered phenol, a hindered amine lightstabilizer, a benzotriazole, a thioester, a second phosphite, a metalstearate and a hydrotalcite.
 14. An alkylphenol-free liquid polymericpolyphosphite which comprises:

wherein each R¹, R², R³ and R⁴ can be the same or different andindependently selected from the group consisting of C₁₂₋₂₀ alkyl, C₁₂₋₂₂alkenyl, C₁₂₋₄₀ cycloalkyl, C₁₂₋₄₀ cycloalkylene, C₁₂₋₂₀ methoxy alkylglycol ethers, and Y—OH as an end-capping group; each Y is independentlyselected from the group consisting of C₁₋₂₀ alkyl, C₆₋₄₀ cycloalkyl,C₇₋₄₀ cycloalkylene, C₂₋₄₀ alkylene, C₃₋₂₀ alkyl glycol ethers, C₃₋₄₀alkyl lactone, and —R⁷—N(R⁸)—R⁹—; R⁷, R⁸ and R⁹ are independentlyselected from the group consisting of C₁₋₂₀ alkyl, C₂₋₂₂ alkenyl, C₆₋₄₀cycloalkyl, C₇₋₄₀ cycloalkylene, and H; m is an integral value rangingfrom 2 to 100 inclusive; and x is an integral value ranging from 1 to1,000, and further wherein said polymeric polyphosphite is a reactionproduct of: at least one monohydroxy-terminated reactantselected fromthe group consisting of R¹—OH, R²—OH, R³—OH and R⁴—OH; and at least onedihydroxy-terminated reactantselected from the group HO—Y—OH; and atrifunctional reactant comprising at least one phosphorus moiety, saidpolymeric polyphosphite having less terminal hydroxy groups than saidreaction product formed using dihydroxy-terminated reactants.
 15. Thepolymeric polyphosphite of claim 14 wherein said polymeric polyphosphiteis not based on either an aromatic phenol or an alkylphenol.
 16. Thepolymeric polyphosphite of claim 14 wherein said polymeric polyphosphiteis comprised of a polyalkylene glycol.
 17. The polymeric polyphosphiteof claim 16 wherein said polyalkylene glycol is selected from the groupconsisting of polyethylene glycol and polypropylene glycol.
 18. Thepolymeric polyphosphite of claim 14 wherein each R¹, R², R³ and R⁴ arealiphatic and wherein said polymeric polyphosphite further comprises analkanolamine.
 19. The polymeric polyphosphite of claim 1 wherein saidpolymeric polyphosphite has a weight % P ranging from approximately 3.7%to 8.9%.
 20. The polymeric polyphosphite of claim 19 wherein saidtrifunctional reactant comprising at least one phosphorus moiety isaromatic.
 21. The polymeric polyphosphite of claim 6 wherein saidpolymeric polyphosphite has a weight % P ranging from approximately 3.7%to 8.9%.
 22. The polymeric polyphosphite of claim 21 wherein saidtrifunctional reactant comprising at least one phosphorus moiety isaromatic.
 23. The polymeric polyphosphite of claim 14 wherein saidpolymeric polyphosphite has a weight % P ranging from approximately 3.7%to 8.9%.
 24. The polymeric polyphosphite of claim 23 wherein saidtrifunctional reactant comprising at least one phosphorus moiety isaromatic.
 25. A process for making an alkylphenol-free liquid polymericpolyphosphite which comprises:

wherein each R¹, R², R³ and R⁴ can be the same or different andindependently selected from the group consisting of C₁₂₋₂₀ alkyl, C₁₂₋₂₂alkenyl, C₁₂₋₄₀ cycloalkyl, C₁₂₋₄₀ cycloalkylene, C₁₂₋₂₀ methoxy alkylglycol ethers, and Y—OH as an end-capping group; each Y is independentlyselected from the group consisting of C₁₋₂₀ alkyl, C₆₋₄₀ cycloalkyl,C₇₋₄₀ cycloalkylene, C₂₋₄₀ alkylene, C₃₋₂₀ alkyl glycol ethers, C₃₋₄₀alkyl lactone, and —R⁷—N(R⁸)—R⁹—; R⁷, R⁸ and R⁹ are independentlyselected from the group consisting of C₁₋₂₀ alkyl, C₂₋₂₂ alkenyl, C₆₋₄₀cycloalkyl, C₇₋₄₀ cycloalkylene, and H; m is an integral value rangingfrom 2 to 100 inclusive; and x is an integral value ranging from 1 to1,000, and further wherein said steps comprise: adding at least onemonohydroxy-terminated reactant selected from the group consisting ofR¹—OH, R²—OH, R³—OH and R⁴—OH; and adding at least onedihydroxy-terminated reactantselected from the group HO—Y—OH; and addinga trifunctional reactant comprising at least one aromatic phosphorusmoiety.
 26. The process of claim 25 which further comprises the step of:adding an alkanolamine.
 27. The process of claim 25 which furthercomprises the step of: adding a carbon-based polymer.
 28. The process ofclaim 27 which further comprises the step of adding at least one otheradditive selected from the group consisting of a hindered phenol, ahindered amine light stabilizer, a benzotriazole, a thioester, a secondphosphite, an alkanolamine, a metal stearate and a hydrotalcite.